AU604828B2 - Monomers and initiators for group transfer polymerization - Google Patents

Description

000000_ if

I

t P/00/0 11 PATENTS ACT 1952-1973 60482 Form COMPLETE

SPECIFICATION

(ORIGINAL)

FOR OF~FICE USE Class: Int. CI: Application Number: Lodged: Complete Specification-Lodged: Accepted: Published: This document contnlins thle aimendments made uinde1r Sction1 49 and is correo.t for printing, 0 Priority: ro:Related Art: Name of Applicant: h.

4 4 ot Address of Applicant: Actual Inventor: Address for Service: TO BE CWUMPL$TED BY APPLICANT DU PONT DE NEMOURS AND COMPANY., a corporation organized and existing under the laws of-the State of Delaware, of Wilmington, Del~aware, 19898, United States of America.

Waltuer Raymond 1-ERTLER Care of JAMES M. LAWRIE CO., Patent Attornieys of 72 Willsmero Road, Kew, 3101, Victoria, Australia.

Complete Specification for the invention entitled: MONOMERS AND INITIATORS FOR GROUP TRANSFER POLYMERIZATION The following statement Is r, full description of this invention, Including the best method of performing It known to Note: The description Is to be typed In doUble spac .Ing, pica type face, In an area not exceeding 250 mmn In depth And 160 mm In w'aith, on tough while paper of, good quality and It Is to be Inserted Inside this formi.

11710/16-L 1 1710/76-L j fi gIoot',I. 11nt~n..ii ~'cn tcfi'tlfIC.crj 1A

TITLE

Monomers and Initiators for Group Transfer Polymerization BACKGROUND OF THE INVENTION Field of the Invention This invention relates to Group Transfer Polymerization, to selected polyenoate compounds which are useful as monomers therein, and to selected Spolyenolate compounds which are useful as initiators therein.

Background S: t United States Patents 4,414,372; 4,417,034; 4,508,880; 4,524,196; 4,581,428; 4 5 8 8,795; 4,598,151; 4,605,716; and 4,622,372; 4 i i ~Z-ni r tedlS-ta T. atn4 ppli-a.-t ne o-r ia! 1 5 8--fi-c Octoer18 -No ember 2-1 184-;- 1-0-1----ed-Oe-tber---51---98- 2- 4 n- f-led-- as4n-e 1 &6- 1 referred to hereinafter as "the aforesaid patents and patent the presence of: an initiator having at "least one initiating site and which is a tetracoordinate organo(Si, Sn or Ge) compound, including such compound having at least one oxygen, nitrogen or sulfur atom attached to the Si, Sn or Ge; and (ii) a co-catalyst which is a source of fluoride, bifluoride, cyanide or azide ions or a suitable Lewis acid, Lewis base or selected oxyanion.

Such polymerization processes have become known in Sthe art as Group Transfer Polymerization (Webster et al., "Group Transfer Polymerization A New and versatile Kind of Addition Polymerization", J. Am.

Chem. Soc. 105, 5706 (1983)).

CR-8359 1A 2 Preferred monomers for use in Group Transfer Polymerization, hereinafter referred to as "Group Transfer Polymerization acrylic monomer(s)", are selected from acrylic and maleimide monomers of the formula CH 2 -C(Y)X and CH== -CH I

I

O--C C--O and mixtures thereof,

N

R

wherein: SX is -CN, -CH-CHC(0)X' or Y is -CH 3 -CN or -CO 2 R, provided, t however, when X is -CH-CHC(O)X', Y is 15 -H or -CH3; t" X' is -OSi(R -OR or -NR'R"; Seach R1, independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing 4j up to 20 carbon atoms or provided that at least one R 1 group is not -H; S4 R is: a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; a polymeric radical containing at least 20 carbon atoms; a radical of or containing one or more ether oxygen atoms within aliphatic segments thereof; a radical of or (c) containing one or more functional substitu\ents that are unreactive under T

I

4£ 4 It 4-4 I I .444 4-4 4 4 45£ -444 3 polymerizing conditions; or a radical of or (d) containing one or more reactive substituents of the formula 1 -C wherein Y 1is -H or -CH 3 and ZI is 0 or NR' wherein RI is as defined below; and each of R' and Roo is independently selected from C 1 4 alkyl.

Preferred initiators are selected fromn tetracoordinate organsilicon, organotin and organogermanium compounds which may be represented by.

the formulas QIMZ, QIM(Z1) 2 and (ZI M] 0 wherein: each Q1, independently, is selected from -R1,-OR 1, -SR 1and -N(R 1 2 1s Z is an activating substituent selected from the group consisting of -4-4 -4 44554-4 -CN, -C-C;N, 13 R 2 0 13

R

0 R2 It

I

Y Zi 0 R2 'it 'SCH 2 n 4' '4 4 4-4 4 4 4 -4 1 3 -N-C-C-l -0Cw=C-R 2 12 13 x R LCnM 2 4,3- II 4

-OC=.-CR

2

-SR

6

-OP(NR'")

2 -OP(OR I)2

CH

2 n -OP(OSi(R )312 and mixtures thereof; 2 is -OSi(R1)3 -R -OR 6 or -NR'R";

R

6 is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; S(b) a polymeric radical containing at i *least 20 carbon atoms; J a radical of or containing Sone or more ether oxygen atoms within aliphatic segments thereof; i a radical of or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; or a radical of or (d) containing one or more initiating s 4 tes; each of R 2 and R 3 is independently selected from -H and a hydrocarbyl or polymeric 6 radical, defined as for R above; subparagraphs to R, R and Z' are as defined above for the monomer; m is 2, 3 or 4; n is 3, 4 or 1 is -OC-C--R 2 wherein R 2 and R 3 1213 X R are as defined above;

R

2 and R 3 taken together are -4b?

HI

H

3 C

CH

3 3 provided

CH

3

R

2 0 I II Z is -C-CX 2 or -C-C(R )(R 3

SR

3 X 2

X

2 and either R or R 3 taken together are 0 0 °tI O 0 S6 "C provided 1t itt 1

II

Z is -C-CX 2 or -OC=C(R 2

)(R

3 and 3 2 R X M is Si, Sn, or Ge.

Preferred initiators are those wherein M is Si.

Preferred co-catalysts are selected from a source of bifluoride ions HF 2 a source of fluoride, cyanide or azide ions; a source of oxyanions, said oxyanions being capable of forming a conjugate acid having a pKa (DMSO) of about 5 to about 24; a suitable Lewis acid, for example, zinc chloride, bromide or iodide, boron trifluoride, an alkylaluminum oc- 'q or an alkylaluminum choride; or a suitable Lewis base, for example, a Lewis base of the formula selected from (R) 3 M' and 5

R

X R N wherein: M' is P or As; '4

I

6 1 X is or -CH, provided, however, when the monomer is a nitrile, X is -CH; each R 4 independently, is: a C 1 12 alkyl, C 4 12 cycloalkyl,

C

6 12 aralkyl or di(Cl_ 4 alkyl)amino group; a group of wherein two or three of the alkyl, cycloalkyl and/or aralkyl groups are joined together by means of one or more carbon-carbon bonds; a group of or wherein the i alkyl, cycloalkyl and/or aralkyl groups i ,contain within aliphatic segments I thereof one or more hetero atoms selected from 0, N and S; or a group of or wherein the alkyl, cycloalkyl and/or aralkyl groups contain one or more substituents that are unreactive under polymerizing conditions; and each R is -CIICH 2 or -CH 2

CH

2 containing one or more alkyl or other substituents that are unreactive under polymerizing conditions.

Additional details regarding Group Transfer Polymerization can be obtained from the aforesaid patents and patent applications, the disclosures of which are hereby incorporated by reference.

Numerous polyenoates containing two or more conjugated double bonds are disclosed in the art.

I Silyl enolates containing up to three conjugated double bonds are also known, and polyunsaturated silyl enolate initiators for "living" polymerization are generically disclosed in the aforesaid patents and patent applications. Polymers of conjugated I C'L~i""i -i I I

I

7 polyenoates prepared by conventional polymerization methods are also known in the art, and the preparation of "living" polymers from polyenoate monomers by silicon-initiated polymerization is disclosed in the aforesaid patents and patent applications, the polyenoate monomers being of the formula

CH

2 =C(Y)CH-CHC(O)X' wherein Y is H, CH 3 CN or CO 2

R

and X' incl'udes OR wherein R is defined as above.

It is an object of the present invention to provide processes for preparing internally and/or terminally unsaturated "living" polymers by polymerizing one or more selected polyenoate monomers fo in the presence of a tetracoordinate organosilicon, I organogermanium or organotin initiator and a suitable 0Oo co-catalyst. A further object of the invention is to 0 015 provide polyenolate initiators and polyenoate t 004 monomers which are useful in Group Transfer Polymerization. Another object of this invention is to provide "living" polymers, solutions, coatings and shaped articles prepared therefrom, processes for ,0 20 quenching the "living" polymers, and solution or 'dispersion coat 4 ngs and adhesives and shaped articles prepared from the quenched polymers. These and other objects will become apparent from the following description of the invention.

DETAILED DESCRIPTION OF THE INVENTION c The invention herein resides in the process of preparing a "living" polymer having internal and/or terminal unsaturation by contacting under polymerizing conditions at least one acrylic monomer with a tetracoordinate organosilicon, organotin or organogermanium polymerization initiator containing at least one initiating site, and (ii) a co-catalyst which is a source of bifluoride, fluoride, cyanide or azide ions, or a suitable (bi)oxyanion, Lewis acid or Lewis base, the process further characterized in that: the monomer comprises one or more polyenoate compounds of the formula CH(R 2)-C(R 3)fC(R 4)-C(R 5Hn or (ii) the inlt$,ator comprises one or more polyenolates of the formula Q 2 -C(R 3

)-C(R

4 HQ 1 or C-silylated isomers thereof; or (iii) the monomer comprises one or more polyenoate compounds of the formula CH(R2)=C(R 3){-C(IR4)C(n )Hn--C(O)X and the initiator comprises one or more polyenolates of the formula p4 44 Q fC(R 3 )4nQ 1 or C-siiylated isomers thereof 7 15(a) -H or "tot a hydrocarbyl radical which is an p t aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical, containing up to 20 carbon, atomsa polymeric hydrocarbyl radical 4 containing at. least 20 carbon atoms; a radical of or containing one or more ether oxygen atoms within aliphatic segments ther( a radical of (c con- U taining one or, more functla,_", substituents that are inert Unider polymerizing condit ions; each of R 3 UR 4 and RS, independently,, is -H or a radical, as defined In (d ad e)fo 2 orRan h (d an 3e fo511o n h closest R 4, or 11 and the closest R or the two closest R 4 5roups,, or the two closest R5groupz# tgkoon together, form a ring structure Iconainn at 1044t

~I

9 carbon atoms or at least 5 carbon atoms 4 and a heteroatom selected from -Nand the heteroatom being substituted with R' defined as below; X is -OR or -NR'R"; R is a radical as defined in (d) and for R 2 or R and the closest R 5 taken together, form a 5- to 8-membered lactone ring; each of R' and independently, is C 1 4 alkyl; and

S

n is an integer and is at least 1; Sprovided, however: 2 when n is 1, at least one of R ;i R and R is hydrocarbyl; i5 (ii) the number of R 2 5 hydrocarbyl substituents does not exceed the number of -C-C- Sdouble bonds; (iii) a carbon atom substituted with S2- 5 hydrocarbyl is not adjacent to more than one 20 other carbon atom substituted with R 2 5 hydrocarbyl, hydrocarbyl in (ii) and (iii) being as defined above in and for R 2 Q1 is -C(R )-C(OM[R1I Q is -C(R C) OM[R 1 or X' is -OSi(R -OR or -NJ'R"; 1 each R independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic, or mixed aliphaticaromatic radical containing up to carbon atoms; and 4. M is Si, Sn or Ge; provided, however, in the initiator of the formula 2 3 4 1 Q 2C(R HnQ or C-silylated isomers thereof not more than one of R and the closest R 4 is hydrocarbyl; and when Q2 is -C(R2)C(X')OM(R 1 not I I k4 more than one of R and the adjacent R is hydrocarbyl.

Preferably, R or R more preferably R is hydrocarbyl. Preferably, hydrocarbyl in R and R 2 is methyl or ethyl, more preferably methyl; X' is -OR; and n is 1-3.

The "living" polymer prepared by the invention process comprises: A, at least three repeat units of the formula -CH(R2 C(R3)-C(R or (ii) at least three repeat units of a SGroup Transfer Polymerization acrylic monomer; or (iii) a mixture of at least three repeat units of and (ii); each of (ii) and (iii) containing -M(R )3 moieties (from the initiator) at "living" ends of the polymer chains; and the initiator residue, that is, after removal of -M(R )3 from the initiator, at non-living ends of the polymer chains, said residue comprising a saturated hydrocarbyl radical or the unsaturated moiety R2+C(R 3)C(R 4nC(R 5 provided, however, the initiator residue is the unsaturated moiety when the "living" polymer contains only repeat units and B. when Q2 in the polyenolate initiator is other than R 2 central segments of the formula

R

2 3 4 5 I I I I c o x I I COX' COX wherein: hydrocarbyl radical is as defined in in R 2 above; X' is -OSi(R 1 )3 -OR or and 11 M, R, R 5 X and n are defined as above; It will be understood from the description herein that the process of .he present invention may employ polyenoate or Group Transfer Polymerization acrylic monomers, the latter being as defined hereinabove, and/or polyenolate or Group Transfer Polymerization initiators, that is, a tetracoordinate organosilicon, organotin or organogermanium polymerization initiator containing at least one initiating site, provided that, if only a Group Transfer Polymerization acrylic monomer is used, the o°0 initiator must include the polyenolate compound defined above and, if only a Group Transfer Polymerization initiator is used, the monomer must 15 include the polyenoate compound defined above.

The invention also resides in solutions of the "living" polymer, in coatings and shaped articles prepared therefrom, in a process of quenching the "living" polymer with an active hydrogen source, and S, 20 in solution and dispersion coatings and adhesives and in shaped articles prepared from the quenched L! polymer.

The polyenoate monomers and polyenolate initiators employed in the present invention are believed to be known or obvious compounds.

Catalysts, solvents, concentrations of reactants and catalysts, process conditions and optional additives, such as polymer life enhancement agents and/or chain transfer ac7ents, employed in the present process are those described in the aforesaid patents and patent applications, the disclosures of which have been incorporated herein by reference.

Preferred catalysts are sources of bifluoride ions or oxyanions.

112 When employing both the polyenolate initiator and the polyenoate monomer of the invention, it is preferred to employ a polyenolate initiator whose structure most closely matches that of the polyenoate monomer.

The polyenolate initiators of the aforesaid formula are either available commercially or are prepared from the monomers of the invention, or related polyenoates, by known methods, such as those described by I. Fleming et al.,Tetra. Lett., 34, 3205 (1979), or (ii) N. R. Long et al., Syn. Comm., 11, 687 (1981), by reaction with a hydrogen-donating compound of the formula (R 3 M-H, or by reacting the lithium enolate with a suitable organosilicon, organogermanium or organotin compound such as those 1 1 15 of the formula (R 3 M-Cl, wherein R and M are as t. defined above.

It will be understood that the initiators of the aforesaid formula are mono- or difunctional depending on Q2, and that the latter are useful for preparing polymers wherein both ends are "living", j from which coupled or block polymers can be prepared.

It is further contemplated that such initiators may contain additional initiating sites at the ends of hydrocarbyl substituents, and/or functional groups which Oan be used to prepare branched, star, block or cross-linked polymers.

The polyenoate monomers employed in the process of this invention are mono- or diesters or derivatives thereof, such as amides or lactones, having at least two conjugated double bonds. The monomers may contain hydrocarbyl substituents and, optionally attached thereto, functional groups which, although inert during "living" polymerization, can be used to post-react the virgin polymer to provide branched, block, graft, ladder or cross-linked 12 I I i 13 polymeric products. Moreover, such featurez will be supplemented by functions provided by the initiator, residua of which are chemically bound to the polymer of the invention, as described in the aforesaid patents and patent applications.

The polymers of the present invention are "living", that is, they contain terminal (R )M initiating moieties (at the "living" ends of the polymer chains), and can be capped, or further polymerized in the presence of catalyst by the addition of more of the same or a different active monomer. The virgin polymers can be further Sconverted into branched, block, graft, ladder and/or cross-linked structures depending on the distribution of "living" (initiating) sites and functignal groups as described above. Moreover, the polymers are internally and/or terminally unsaturated (if, respectively, the monomer is a polyenoate and/or if the initiator is a polyenolate), said unsaturation being useful for cross-linking and/or otherwise chemically modifying the polymer.

Coatings and films can be cast from solutions of the "living" polymers of the invention.

Alternatively and preferably, the "living" polymers can be quenched by treatment with an active hydrogen source as described in the aforesaid patents and 4, patent applications. The quenched polymers are useful for preparing shaped articles and solution or dispersion formulations which are useful for coating or adhesively bonding a wide variety of substrates, including metals, cellulosics (wood and paper), glass and plastics.

Polymers prepared in the present invention differ morphologically from those prepared by hnown prior art methods, For example, poly(ethyl sorbate) obtained in the present process is a viscous fluid *12 14 14 havinn a glass transition temperature (T of 11.7 0

C,

in contrast to the known stereoregular crystalline poly(ethyl sorbate) having a melting point (Tm) of 175*C and prepared by anionic polymerization (G.

Natta, M. Farina, P. Corradini, M. Peraldo, M.

Donati, and P. GAnis, Chimica Ind., Milano, 1960, 42, 1361). Because many of the dienoate polymers prepared by the present process have T s below ambient temperatures, they are especially useful as adhesives. Acrylic polymers prepared with a dieneor triene- initiator of the invention have terminal vinyl or butadienyl groups and are useful for grafting, via free radical polymerization, to give block or comb polymers. Example 16 D herein demonstrates the copolymerization of butyl 5 methacrylate with the butadiene-ended poly(methyl methacrylate) macromonomer prepared by initiation of methyl methacrylate with a hexatriene-initiator.

Example 17 herein demonstrates the initiation of methyl 2-methylpentadienoate polymerization with the difunctional initiator Me 3 SiO OSiMe 3 the curved MeO OMe line indicative of the fact that various stereoisomers are present.

Homopolymerization of diethyl muconate by the present process is quantitative (Example 21 herein), in sharp contrast to prior art processes,

'I

e.g. Y. Bando et al. J. Polymer Sci., Polymer Chem.

Ed., 15, 1917 (1977), in which radical and anionic (n-butyl lithium initiator) polymerization gave low conversion of diethyl muconate to 1,4-trans polymer.

4i

I--

In the following examples which provide Spreferred embodiments of the invention process, number and weight average molecular weights of the polymer products (M M were determined by gel permeation chromatography (GPC). The polydispersity of the polymer is defined by D M/Mn. Unless otherwise specified, the "living" polymer products were quenched by exposure to moist air or methanol prior to molecular weight determination. Parts and percentages are by weight and temperatures are in degrees Celsius unless otherwise specified.

Example 1 i o Polymerization of Ethyl Sorbate 4a STo a solution of 0.1 mL (0.5 mmol) of 0. [(l-methoxy-2-methyl-l-propenyl)oxy]trimethylsilane 4 (MTS), and 10 pL of 0.1M tetrabutylammonium m-chlorobenzoate/THF in 20 mL of THF was added 7 g S<o (7.3 mL, 50 mmol) of ethyl sorbate which had been Spurified by passage over a column of neutral alumina b o Sunder argon. No exotherm was observed, so 50 p7 of additional catalyst solution was added, leading to a Sslow rise in temperature of 100 during 30 minutes.

One hour after the end of the exotherm, a sample was removed for analysis. NMR showed that conversion to 1 o 25 2.5* poly(ethyl sorbate) was 100%. GPC showed Mn 18,700, SM 36,300, D 1.97; M theoretical 14,100 measured "w n against a PMMA standard. Addition of 3.7 mL of ethyl sorbate gave a slow 20 exotherm. NMR showed that of the second monomer charge was converted to polymer, M 29,800 (theory for 35% corversion of second charge 16,550), Mw 58,800, D 1.97. The polymer was isolated by twice precipitating into hexane to give 4 g of rubbery poly(ethyl sorbate).

Vapor phase osmometry (VPO) MW in toluene 24,500.

I i ~1 16 IR: 975 cm (trans CH-CH). ~]0.3759 (chlorollorm, 250). Differential scanning colorimetry (DSC): T g 11.70. NMfl: 0.90 ppm (mn, 3H1, backbone CH 3 1.2 (mn, 3H, CH 3 of ethyl), 2.3-3.3 (mn, 2H, CH), 4.05 (mn, 2H, 0CH 2 5.35 (broad s, 2H1, HC=CH).

Example 2 Preparation of Block Copolyner of Methyl tiethacrylate (MMA) and Et-hyl Sorbate TO a solution of 90 PL (0.43 inmol) of MTS and 10 uL of 0.1M tetrabutylamnoniun i-chloro-, benzoate/tetrahydrofuran (THF) in 10 mL of THF was added 3.2 ML (30 imnol) of MMA. After adding 10 pL of additional catalyst solution, the temperature rose to 44a. A sample was removed for GPC analysis which showed R1 6420 (theor. 7000), Ri 8230? D 1.28 n w Then 7.3 mL (50 mmol) of ethyl sorbate was added, and following addition of an additional 20 pL of catal,,yst solution, the temperature slowly rose to 460. GPC analysis of a sample showed R~ 17,600 (theor.

n K 23,300), R4 29,400, D 1.68. The addition of 3.2 iI U w of MMA along with 30 kgL of additional catalyst solution gave only a slight exotherm. Precipitation twice into hexane gave 9.5 g of tacky polymer, 119,600, Ri 33,400, D 1.71, ~ih0.299 n w n (chloroform, 250). DSC showed a T at 90, and on g reheat at 17.70,, NMR showed that the polymer consisted of 52 mole ethyl sorbate units and 48 mole MMA units.

Example 3 Polymerization of Ethyl 2-Methylpentadienoate

(EMPD)

To a solution of 40 uL (0.2 inmol) of MTS and 5 pL of 0.114 tetrabtvtylainmonium m-chlorobenzoate/ TIIF was added 4 g (4.35 mL, 28.5 inmol) of distilled ethyl 2-iethylpentadienoate. No Oxothern occurred, C i ii 17 so 40 pL of additional catalyst solution and 20 uL of additional MTS were added with no exotherm. Addition of 10 pL of catalyst solution gave a yellow color but no exotherm. Upon'addition of 50 pL of MTS (0.25 mmol) the temperature rapidly rose to 520 and the solution became viscous. NMR showed that the conversion to polyEMPD was 100%. The solution was quenched with 1 mL of methanol, and the gummy polymer was precipitated with hexane. The polymer was dissolved in methylene chloride, washed with brine, dried (magnesium sulfate), and evaporated to 3.5 g of S' rubbery polyEMPD. GPC: Mn 52,600 (theoi:. 16,000), Mw 228,000, D 4.33 DSC: T NMR: 1.17 (s, g 3H, a CH3), 1.24 J-7 Hz, 3H, CH 3 of Et), 2.18 (m, J-14 Hz, 1H, chain CH2), 2.46 J- 7 Hz, 1H, chain

CH

2 4.10 J-7 Hz, 2H, CH 2 of Et), 5.02 J-16 Hz, 1H, trans C-CH), 5.36 t, J=16 Hz, J-7 Hz, 1H, C-CH). IR (film from chloroform): 1730 cm-1 (saturated ester 975 cm 1 (trans HC=CH).

0.9605 (chloroform, UV: End absorption only.

Example 4 Preparation of Block Copolymer of Methyl Methacrylate and Ethyl 2-Methylpentadienoate To a solution of 60 pL (0.3 mmol) of MTS, and 70 pL of 0.04M tetrabutylammonium biacetate/THF was added 2.2 4iL (20 mmol) of MMA. After the end of the exotherm, analysis of a sample of the solution Sshowed 100% conversion to PMMA of Mn 6660 (theor.

6760), M 7430, D 1.12. Then, 6 g (6.5 mL, 42.75 mmol) of ethyl 2-methylpentadienoate, which had been stored over molecular sieves, was added dropwise.

The exotherm reached 410, but the temperature fell during the addition of the final 2 mL of EMPD feed.

Analysis of the solution showed some residual EMPD.

f 18 The polymer had M 24,200 (theor. 26,760), M 51,200, D 2.12. The GPC curve was bimodal, indicating about 10% of the polymer was about 9000 MW (probably unreacted PMMA homopolymer). The polymer was isolated and washed as in Example 3 to give 5.3 g of elastomeric polymer. NMR analysis of the polymer showed it to consist of 60 mole EMPD units and mole MMA units, Example A. (E,E,E)-3(2,4-Hexadien-l-ylidene)-4,5-dihydro- 3(3H)-furanone ("OTL") In a reaction flask fitted with a Aechanical stirrer was placed 5.05 g of 60% sodium hydride dispersion in mineral oil (0.126 mol). The sodium hydride was then washed three times with toluene, removing the toluene with a filter stick.

Then, 330 mL of toluene was added, followed by 28 g i} (0.126 mol) of a-diethylphosphono-y-butyrolactone, 1 prepared by the method of K. H. Buchel, H. Rochling, F. Korte, J. Liebig's Ann. Chem., 1951, 10, 685.

ti When the addition was complete, the mixture was stirred at 50-600 until hydrogen evolution had ceased (about 30 min.). After cooling to 200, 12.12 g (13.9 mL, 0.126 mol) of sorbaldehyde was added.

After stirring at 800 for 2 hours, the mixture was filtered hot, and the filtrate was evaporated under i reduced pressure. The residual oil (18 g) gradually crystallized. Recrystallization from carbon tetrachloride-heptane gave 5.4 g of pale yellow crystals, m.p. 94-980, of OTL. Recrystallization Sfrom toluene-heptane gave 2.5 g of OTL, m.p. 94-99o.

UV (chloroform): 315 nm 39,100). IR (chloroform): 1745 cm (conj. 5-embered iactone), 1650, 1625 cm (conj. NMR (chloroform-d, 360 mHz): 1.84 (d, J-6 Hz, 3H, CH 3 2.98 (t of d, J37 Hz, Jallylic-3 I Y; 19 Hz, 2H, CH 2 4.40 J-7 Hz, 2H, OCH 2 5.99 (d of q, Jtrans-1 5 Hz, Je- 6 Hz, IH, vinyl H-7), 6.1-6.3 2H, vinyl H-5 and 6.57 (d of d, 15 Hz, JH3 12 Hz, 1 H, vinyl 7.1 (d of t, JH42 Hz, allylic3 Hz, 1H, vinyl H-3).

A sample of OTL of greater purity was obtained by sublimation at 85-90°/0.1 mm. This gave colorless crystals with m.p. 99.5-100.5°.

Anal. calcd. for C 10

H

12 0 2 C 73.15; H 7.37.

Found: C 71.31; H 7.21.

i00 B. Polymetization of OTL with MTS and Tetrabutylammonium Acetate tetrabutylammonium acetate/THF. No exotherm was observed, so an additional 120 L of catalyst solution was added, leading to an amber color formation and a slow 20 exotherm. A precipitate formed. NMR analysis of the reaction mixture showed no residual monomer. The mixture was filtered and the filter cake was washed with THF to give 0.48 g of colorless solid polymer, poly(OTL). Evaporation of the filtrete and suspension of the residue in hexane and filtration gave 0.58 g of brown polymer. The NMR spectra of the two polymer samples were nearly identical, the polymers differing only in molecular weight. GPC analysis of the THF-"insoluble" poly(OTL) (from which part of the sample had to be removed by filtration in order to make up the 0.25% solution in THF for GPC) showed M 7240, M 10,900, n w D 1.51. The soluble poly(OTL) fraction had M 1850, Mw 9350, D 5, with about 2% Mn 2,551,000, Mw 8,706,000, D 3.41. The "insoluble" poly(OTL) was readily soluble in methylene chloride, chloroform, and 1,2-dichloroethane, but insoluble in THF and toluene. The polymer tenaciously retained THF, which could be removed only after 2 days at 50-700/0.1 mm.

The polymer also retained the trimethylsilyl group as evidenced by the NMR spectrum, permitting calculation of a Rn of 10,000. NMR (chloroform-d, 360 mHz): 0.14 3H, SiMe), 1.05 3H, Me), 2.0-2.4 2H, 1 C-methylene), 2.55-2.7S 1H, CH), 4.14-4.24 (m,m, 2H, O-CH 2 5.5-5.7 2H, C-CH), 6.0-6.22 2H, C-CH). UV (chloroform): 251 nm 17,800) consistent j 15 with conjugated diene, probably cisoid. DSC: First heat shows exotherm peaking at 143.90. Reheat shows no exotherm at 143.9°, but instead, a well-defined T g at 150.20. TGA shows onset of rapid weight loss at 370.2°.

Example 6 Preparation of Block Copolymer of Methyl Methacrylate and Ethyl Sorbate o a solution of 0,4 mL (2 mmol) of MTS and 52 pL (0.4 mmol) of bis(dimethylamino)methyl phosphine in 10 mL of propylene carbonate was added 5.4 mL (50 mmol) of methyl methacrylate. After a delay, the exothermic polymerization caused the temperature to rise to 560. A sample was removed for analysis by GPC: M 3150 (theor. 2600), RM 4320, n w D 1.37. Then, 14.6 mL (100 mmol) of ethyl sorbate was added, followed by 10 mL of propylene carbonate and 104 uL (0.8 mmol) of bis(dimethylamino)methyl phosphine. A slow exotherm of 1.50 was observed.

After 3 h a sample removed for analysis showed some 21 residual ethyl sorbate monomer, and polymer with bimodal molecular weight: 96% R' 5470 (theor. 9600) n R w7640, D -1.40, and 4% R n 191,000, R w 353,000, D 1.85. Then, 5.4 nib: mmol.) of methyl methacrylate was added producing a slight exotherm.

After 18 h analysis of a sample showed residual zesrhyl methacrylate and polymer with 96% R 6470 (theor. 12,100), R1 9650, D 1.49; 4% Ri 190,000, Mw w n 305,000, D 1.60.. Little of the second methyl methacrylate block was formed. The gummy polymer was precipitated into 1:1 methanol-water, redissolved in :tetrahydrofuran and again precipitated with 1:1 'water-methanol. The polymer was thnm dissolved in methylene chloride and washed with aqueous sodium chloride solution, dried (magnesium sulfate) and evaporated to 4.7 g of flexible polymer. NMR showed the composition of the block copolymer to be 54 mole .1 methyl 'iet Acryjate units and 46 mole ethyl sorbate units, i~8940, i'iw 23f2001 0 2.59.

Example 7 Polymerization of Methyl 2-Methylpentadienoate with I-Ethoxy-l-trimethylsiloxy-1,3-.butadiene (Batch Process) To a solution of 6.6 mL (50 minol) of methyl 2-inethylpentadienoate (prepared by the method of H. 0. House, G. H. ]Rasmusson, J:i. Org. Chem. 1961, 26, 4278, and purified over a short column of neUttal alumina under an argon atmosphere) and 10 p4L of 0.IM trit(dimethylamino)sulfonium bifluoride (TAS bifluoride)/acetonltrile in 50 mL of tetrahydrofurgn was added 55 /pL (0,25 rnmol) of 1ehx~-riehl siloxy-l,3.-butadiene (prepared by the method of I.

Fleming, J. Goidhill, I* Paterson# Tet. LetLt.~ 1979, 34, 3205). When the exothermic polymerization was finished, a sample was removed for analysis: NMR showed no residvik tx4PC of the DL?1IYz-er showed A~ 46,500, A 58,700,, 0 Vapor phase n w osmometry (VPO) in tvbt,'rte showed A 35,000 (theor.

R n 25,200). After quto,,hnq i~th 1 mL of methanol, the polymer was precipitated with hexane, dissolved in methylene chloride, *44i,%ed 'with brine, dried (magnesium sulfa~te) andi ovapoxited to 5.2 g of tacky polymer. DSC showed a T of 2.70 (first heat), 2.80 (on second heat), and -0,60 (on third heating), Thermogravimetric analysis (TGA) showed onset of weight loss at 3250 (in nitrogen) and at 3150 *(in air). NMR of, the polymer (360 Mlliz, chloroform-d) I, clearly shows a 1,4-polymerization and a trans C-C 4: double bond in the polymer backbone. The observed trans vinyl H coupling constant is 16 Hz, and the C-methyl resonance occurs at 1.17 ppm.

Example 8 Poly(methyl 2-methylpentadienoate) as an Adhesive for Glass A sample of poly(methyl 2-methylpentadienoate) from Example 7 was softened with methylene chloride and pressed between two glass plates. After warming at 900 and then cooling, the glass plates remained firmly bonded together by the clear adhesive.

Example 9 Polymerization of Methyl 2-Methylpentadienobte with l-Ethoxy-l-trimtethylsiloxy-d 3-butadiene# (Feed Process) To a solution of 0.22 mL (1 mmol) of l-ethoxy.-1-trimethylsilox y-1,3-butadiene and 50 pL. of 0.1ti tetrabutylammonium, m-chlorobenzoate/TH' in 30 niL of tetrahydcofuran was added 4 niL (30 mmol) of methyl 2-methylpentadienoate at a rate to keep the 23 temperature below 35". Sixty minutes after the end of the exotherm, a sample was removed for analysis: NMR showed no residual monomer, and GPC showed that the polymer had M 8440 (theor. 3900), M 9950, D 1.18. Then, an additional 4 mL (30 mmol) of methyl ',-methylpentadienoate was fed below After 18 h a sample was removed for analysis: NMR showed no residual monomer, and GPC showed that the polymer had Mn 11,800 (theor. 7686), M 16,000, D 1.35. The polymer was isolated by quenching with 1 mL of methanol and evaporating to 7.4 g of viscous .i polymer. Because complete polymerization of monomer occurred after the polymer was allowed to stand for 1 I r h, and there was a correspondng increase in S* molecular weight, it can be concluded that the j 15 polymer must have been "living".

i 4 Example Polymerization of Methyl 2-Methylpentadienoate (Feed Ip n Process) 20 The procedure of Example 9 was followed except that 0.2 mL (1 mmol) of MTS was used in place of l-ethoxy-l-trimethylsiloxy-l,3-butadiene. NMR showed tat there was no residual monomer after both the first and second monomer feeds. GPC after the first feed showed M n 28,300 (theor. 3900), i 53,100, D 1.88, and after the second feed M 33,900 (theor.

7670), M 61,400, D 1.81.

w Example 11 Preparation of Block Copolymer of Methyl J 2-Methylpentadienoate and Methyl Methacrylate To a solution of 0.11 mL (0.5 mmol) of 1-ethoxy-l-trimethylsiloxy-l,3-butadiene and 10 pL of 0.1M TAS bifluoride/acetonitrile in 30 mL of THF was i ,f 24 added 6.6 mL (50 mmol) of methyl 2-methylpentadienoate at a rate 'o keep the temperature below 350.

When the exotherm was over, a sample was removed for analysis. NMR showed no residual monomer, and GPC showed Mn 32,000 (theor. 12,700), Mw 46,000, D 1.44. Then, 5.4 mL (50 mmol) of methyl methacrylate was added. The polymer was precipitated with hexane, dissolved in methylene chloride, washed with brine, dried (magnesium sulfate) and evaporated to 7.7 g of tacky polymer. GPC shows M 27,800 (theor. 22,700), R 49,600, D 1.78. Proton NMR w S* showed the polymer to consist of 20.6 mole methyl iethacrylate units and 79.4 mole methyl 2-methylpentadienoate units.

0 0 15 Example 12 Preparation of Block Copolymer of Methyl Methacrylate and Methyl 2-Methylpentadienoate The procedure of Example 11 was followed 0 except that the order of monomer addition was 04' 20 reversed, and 0.1 mL (0.5 mmol) of MTS was used in place of l-ethoxy-l-trimethylsiloxy-1,3-butadiene.

After the addition of the methyl methacrylate, NMR showed no residual monomer, and GPC showed M 10,500 n (theor. 10,100), M 15,300, D 1.46. There was 25 obtained 10.7 g of block copolymer with n 30,900, M n w S% 1 08,000, D 3.49. A shoulder in the GPC trace indicated that about 20% of the total polymer consisted of unreacted poly(methyl methacrylate) (PMMA) of RM 10,500, with the remainder of the n polymer being block copolymer. NMR analysis showed the composition of the product to be 47 mole methyl methacrylate units, and 53 mole methyl 2-methylpentadienoate units.

K Example 13 Polymerization of Methyl Methacrylate with l-Ethoxy-1-trimethylsiloxy-1 ,3-butadiene To a solution of 0.19 g (0.22 ML, 1 mmol) of l-ethoxy--l-trimethylsiloxy--l,3-butadiene and 10 pL of 1M TAS bifluoride/acetonitrile in 30 znL of THF was added 10.8 mL (100 mmol) of methyl methacrylate at a rate to keep the temperature from rising above A sample removed for analysis showed 93% conversion to poly(methyl methacrylate) with R 18,600 (theory for 93% conversi.on, 9400), R w 25,600, D -1.38.

After quenching with 1 mr.

4 of methanol, the polymer was precipitated with 1:1 methanol-water to give, after drying, 9 g of poly(methyl iethacrylate) with a terminal vinyl group.

Example 14 Identification of the Vinyl End Group in Poly(methyl methacrylate) Initiated With l-Ethoxy-l-trimethylsiloxy-1 3-butadiene To a solution of 0.44 mL (2 minol) of 1-ethoxy-1-trimethylsiloxy-1,3-butadiene and 100 uL N of 0.1tj tetrabutylammonium m-chlorobenzoate/THF in mL of THF was added 1.08 mL (10 mmol) of methyl methacry1ate. After the exothermic oligomerization was over, a sample was removed for analysis. NMR showed that there was no res-dual monomer. After quenching with 0.5 mL of methanol, evaporation gave 0.95 g of poly(methyl methacrylate) as i tacky oligomer. Analysis by proton NMR (360 MHz, chloroform-d) showed: 5.5-5.7 ppm (in, 1H, C=CH)f 4.95-5.1 ppm (in, 2fli C=CH 2 2.85-3.1 ppm (in, lH, C'-CCHCOOR), 4.055 ppm J-7 Hz, 2H, OCH 2 consistent with a terminal vinyl group. There was no resonance characteristic of olefin conjugated to an ir i 26 ester group which would have resulted from initiation 9 at the gamma position of the initiator.

Example Preparation of 1-Ethoxy-l-trimethylsiloxy- 1,3,5-hexatriene To a solution of 21.2 mL (15.28 g, 0.151 mol) of diisopropylamine in 150 mL of THF at 00 was added 0.151 mole of 1.6M n-butyl lithium/hexane.

After 30 minutes at 00, the solution was cooled to -780, and 20.6 g (0.147 mol) of ethyl dienoate was added below Then 16.8 g (19.7 mL, S 0.155 mol) of chlorotrimethylsilane was added. After S' warming to room temperature, the solution was evaporated under reduced pressure, and the residue was treated with anhydrous hexane and filtered under argon. The filtrate was evaporated under reduced pressure, and the residue was distilled in a small Vigreux column to give 24.9 g of l-ethoxy-ltrimethylsiloxy-1,3,5-hexatriene, b.p. 53.60/0.2 mm to 57.20/0.1 mm. The fraction (10.2 g) with b.p.

i 57.10/0.1 mm was used for analysis. NMR (360 mHz, chloroform-d) shows 95% z and 5% E stereochemistry at the substituted double bond: 0.26 9H, SiCH 3

[E

isomer at 0.28 ppm]; 1.31 JC=7.5 Hz, 3H, CH 3

(E

isomer 1.265 ppm]; 3.825 JgB7.5 Hz, 2H, OCH 2

[E

isomer at 3.94 ppm]; 4.46 JE= 10 Hz, 1HD) [E isomer at 4.54 ppm]; 4.825 (dd, JG- 10 HZ, JH= 2 Hz, 1HI); 4.96 (dd, JG= 17 Hz, J=2 Hz, 1HK); 5.95 (dd, Hz, JG=10 Hz, 1HF); 6.375 (ddd, =17 Hz, JI 30 Hz, Jp-10 Hz, 1HG); 6.415 (dd, J 15 Hz, JD-10 Hz, 1HE).

i 27 oQB d1Z (JF e \OCH 2CH 3 B. Polymerization of Methyl Methacrylate To a solution of 0.21 g (0.24 mL, 1 mmol) of l-ethoxy-l-trimethylsiloxy-1,3,5-hexatriene prepared in Part A and 50 pL of 0.1M tetrabutylammonium m-chlorobenzoate/THF in 15 mL of THF was added 5.4 mL (50 mmol) of methyl methacrylate at a rate such that the temperature did not rise above 350. When the exothermic reaction was complete, a i* sample was removed for analysis. NMR showed that there was no residual monomer. GPC showed R 5910 1s 15 *(theor. 5125), I w 6630, D 1.12. After quenching r* 15 with 1 mL of methanol, precipitation with 1:1 methanol-water gave 4.9 g of poly(methyl methacrylate) with a terminal butadiene group, C. Identification of Diene End Group of Poly(methyl methacrylate) The procedure of Example 14 was followed except that 0.42 g (0.48 mL, 2 mmol) of l-ethoxy-lprepared in Part A was used instead of 1-ethoxy-l-trimethylsiloxy- 1,3-butadiene. Evaporation gave 1.0 g of oligomeric poly(methyl methacrylate). The proton NMR spectrum of the product (360 mHz, chloroform-d) shows the presence of 5 vinyl protons: 5.0-5.1 ppm 1H,

C-CH

2 5.11-5.2 ppm 1H, C-CH 2 5.42-5.65 ppm 1H), 5.98-6.30 ppm 2H). There is no indication of resonance characteristic of vi'iyl groups conjugated to an ester. Thus, substitution has occurred at the a-position of the triene rather than the c-position, and there is a terminal diene group on the poly(methyl methacrylate).

28 D. Free-Radical Copolymerization of Butadiene-terminated Poly(methyl methacrylate) and Butyl Methacrylate A mixture of 1.0 g of Pt*IA with a terminal butadiene group prepared in Example 16 (Rn 5910, M 6630, D 1.12), 2 g of freshly distilled butyl methacry).ate (BMA), and 2 mg of azobis(isobutyronitrile) in 10 mL of toluene was heated at reflux while a solution of 10 mg of azobis(isobutyronitrile) in 3 mL of toluene was added dropwise during minutes. A sample removed for analysis showed residual butyl methacrylate (NMR). GPC showed M 3140, R1 9910, D=3.16. The solution was n w a concentrated, and polymer was isolated by precipitation with hexane to gitve 1.3 g of solid polymer. NMR analysis showed a 2:1 molar ratio of MIA:BMA units. Two additional precipitations from methylene chloride with hexane (to remove any butyl lethacrylate homopolymer) gave 0.93 g of block 4 20 copolymer with the same 2:1 molar ratio of PMMA:PBMA, ni 8850, R w 13,900, D -1.57. This R n and molar ratio requires that a single PMMA chain (degree of polymerization: 60) was copolymerized with 30 butyl methacrylate units. This would give a theoretical _Mn of 10,089 in reasonable agreement with the observed 4~4 value of 8850.

Example 16 Polymerization of Methyl 2-Methylpentadienoate with 301,4-Bis(trimethylsiloxy)-l,4-bis(iethoxy)- 301,3-butadiene j4A To a solution of 75 pL of 0.1M tetrabuv.ylammonium m-chlorobenzoate/THF and 0.31 mL (0.29 g, 1 mmol) of (54.5% ZZ, 27.3% EE, 18.2% EZ)-l,4-bis( trimethylsiloxy)-1,4-bis(methoxy)-l,3- 29 butadiene (prepared by the general procedure described by N. R. Long, M. W. Rathke, Synthetic Commun. 1981, 11, 687) in 30 mL of THF was added 6.6 mL (50 mmol) of methyl 2-methylpentadienoate at a rate to keep the temperature from rising above After the exothermic reaction was over, *a sample was removed for analysis. NMR showed no residual monomer. GPC showed R n 25,700 (theor. 6400), M w 41,200, D -1.60. After addition of 1 mL of methanol, precipitation with hexane gave 7 g of soft poly(methyl 2-methylpentadienoate).

Example 17 44 4 Polymerization of Ethyl Acrylate with 1,4-Dimethyl- 0 0 401,4-bis( trimethylsiloxy)-1,3-butadiene To a solution of 0.62 mL (2 mmol) of 1,4dimethyl-1,4-bis(trimethylsiloxy)-1,3-butadiene and 10.8 mL (100 mmol) of ethyl acrylate in 50 mL of THF was added 20 pjL of 1M t ri s(dime thylamino) sul fonium 44bifluoride/acetonitrile. A rapid, exothermic 0 0 0 44 20 polymerization occurred causing the temperature to 'Irise from 240 to 46.70. A sample was removed for 4444*:analysis. NMR showed that 69% of the ethyl acrylate was converted to polymer. GPC showed ~i3160 (theory n for 69% conversion 3550), Ri 5300, D 1.67. After w addition of 1 mL of methanr'l, the solution was 44 evaporated to 7.5 g of viscous poly(ethyl acrylate).

Example 18 Polymerization of Methyl Methacrylate with 1,4- Dimethyl-1,4-bis(trimethylsiloxy)-l1,3-butadiene The procedure of Example 17 was followed using 10.8 mL (100 mmol) of methyl methacrylate instead of ethyl acrylate. in order to obtain an exotherm of only 10, 80 /pL of IM tri s(dime thylamino) 29 t sulfonium bifluoride/acetonitrile was added. After 18 h precipitation with 1:1 methanol-water gave a gummy precipitate, which was dissolved in methylene chloride, dried (magnesium sulfate) and evaporated to 1.6 g of PMMA with Mn 1510 (theory for 16% conversion 900), M 3770, D 2.50.

w Example 19 Polymerization of Diethyl Muconate with 1-Ethoxy-ltrimethylsiloxy-l,3-butadiene 0 To a solution of 2.0 g (10.1 mmol) of diethyl muconate (recrystallized from heptane, m.p.

a 62.50) and 0.22 mL (1 mmol) of 1-ethoxy-l-trimethyli siloxy-l,3-butadiene in 10 mL of THF was added 100 #L a of 0.1M tetrabutylammonium m-chlorobenzoate/THF.

S o 15 15 Rapid exothermic polymerization caused a 100 I t temperature rise to 38.6° with formation of a deep orange color. A sample was removed for analysis.

NMR showed that conversion to polymer was quantitative. GPC showed Mn 1850 (theor. 2100), iM 3330, 20 D 1.80. After addition of 1 mL of methanol, evaporation gave 2.2 g of viscous poly(diethyl muconate). Proton NMR analysis of the polymer shows that it has a 1,4-structure. OSC showed a T of 1 9 -15.80, IR (chloroform): 970 c< 1 (trans -CH=CH-) COOEtCOOE COOEt 31 Example Polymerization of Diethyl Muconate with 1-Ethoxy-ltrimethyl-siloxy-1,3-butadiene To a solution of 7 g (35.31 mmol) of diethyl muconate and 50 uL of 0.1M tetrabutylammonium m-chlorobenzoate/THF in 30 mL of THF were added 60 pL (0.25 mmol) portions of 1-ethoxy-l-trimethylsiloxy- 1,3-butadiene until a slow exotherm indicated that polymerization had begun. A total of 300 pL (1.25 mmol) of initiator was required. An additional 50 pL of 0.1M tetrabutylammonium m-chlorobenzoate/THF was added to obtain a slight increase in polymerization 0 9 rate. After stirring for 18 h, a sample was removed Sfor analysis. NMR showed that conversion to polymer was quantitative. GPC showed M 14,000, M 33,500, n *0 1 5 D 2.39. After addition of 1 mL of methanol, the solution was evaporated to a gummy polymer. The 0 product was dissolved in methylene chloride and precipitated in hexane twice, The polymer was then dissolved in methylene chloride, washed with water, dried (magnesium sulfate), evaporated,and dried at 60°/0.1mm to give 4.8 g of poly(diethylmuconate), with A n 16,900, Mw 35,700, D 2.11. DSC shows a Tg of 15.30. TGA shows the onset of rapid weight loss at 2700 in both air and nitrogen.

Example 21 The following example illustrates preparation of methyl 2-methyl-4-trimethylsilyl- 2-butenoate (a C-silyl isomer of l-methoxy-ltrimethylsiloxy-2-methyl-l,3-butadiene) and initiation of MMA polymerization therewith, 4, r 32 A. Preparation of Methyl 2-methyl-4-trimethylsilyl-2-butenoate To a solution of 94.6 mL (0.675 mol) of diisopropylamine in 750 mL tetrahydrofuran at 00 was added 0.673 mol of n-butyl lithium in hexane (approximately 1.6 keeping the temperature at 0.

After 30 min, the solution was cooled to and 117 mL of hexamethylphosp[ooramide was added. Then g (0,657 mol) of methyl tiglate containing 11% methyl 2-methyl-3-butenoate was added, keeping the temperature below After 30 min at 87.7 c mL (0.69 mol) of chlorotrimethylsilane was added, and the solution was allowed to warm to room temperature.

The solution was evaporated under reduced pressure, o o and the residue was treated with anhydrous hexane and 15 filtered under argon. The filtrate was evaporated under reduced pressure, and the residue was distilled S' in a spinning band column to give 50.2 g of the title Sproduct, b.p. 490/0.55 mm-49 0 /0.35 mm.

NMR (360 mHz, chloroform-d): 0.01 9H, CSiMe), 1.66 J=10 Hz, 2H, SiCH 2 1.74 J=1.8 Hz, 3H, C=CME), 3.68 3H, OMe), 6.9 (tq, J=10 Hz, J-1.8 Hz, 1H, C=CH). 1710 cm 1 (conjugated ester), 1640 cm" I (conjugated U.V. (methyXene chloride): 235 nm (c 15,000).

B. Polymerization of MMA To a solution of 0.19 g (0.21 mL, 1 mmol) of the initiator prepared in part A and 5.4 mL mmol) of MMA (purified by passage over alumina under argon) in 50 mL of anhydrous tetrahydrofuran was added 10 puL of 1i TAS bifluoride/acetonitrile. The temperature of the reaction mixture rapidly rose from 250 to 500. Then the reaction was quenched with 1 mL of methanol and a small sample was removed for analysis. NMR showed that there was no unreacted MMA a 33 present. GPC showed A~ 14,400 (theor. 5100), MR n w 35,600, D-2.47. Precipitation with :1 methanolwater gave 4.95 g of PMA.

Example 22 The following example illustrates the use of a protected functionalized silylpolyenolate initiator to prepare PMMA with a terminal carboxylic acid group (after deprotection).

A. Preparation of 2-Methyl-1,l-bis(trimethylsiloxy)- 1 ,3-butadiene To a solution of 42 ML (0.3 mol) of diiso- 4 o4 A too#propylamine in 500 mL of tetrahydrofuran at 00 was a added 0.3 inol of n-butyl lithium/hexane. After 30 min to t 15 at 00, the solution was cooled to -780, and a solution of 14 g (0.14 mol) of tiglic acid in 50 ML of tetrahydrofuran was added. After 1 h at -780, 38 mL (0.3 mol) of chlorotrimethylsilane was added at -781. After slowly warming to room temperature, the solution was evaporated. The residue was treated with dry hexane, filtered, and the filtrate was evaporated; the residue was distilled in a small spinning band column to give 11.6 g of 2-znethyl-l,lbis( trimethylslloxy)-1 ,3-butadiene, b.p. 370/0.35-.

34LO/0.25 Torr., density 0.86. NIIR (360 mHz in CDCl 3 0.22 (2s, 18H, OSi~le), 1.62 3H, C-CMe), 4.71 (dd J-2 Hz, i1H, C-CH), 4.77 (ddo J-18, J-2 Hz, 1H, C-CH), 6.66 (dd, J-18, J=10 Hz, lH, C-CH).

B. Polymerization of IMA with 2-Methyl-1,1-bls(trimethylsiloxy)-.1,3-butadiene and TAS Bifluoride.

To a solution of 0.8 g (0.93 mL, 3.3 mmol) of 2-mpthyl-ltl-bls(.trirnethylsiloxy)-1,3-butadiene and 10 #uL of IM, TAS bifluoride/acetonltrile in 30 mL of tetrahydrofuran was added 10.8 mL (100 mmol) of 34 MMA. A small exotherm was observed, so an additional pL of 1M TAS bifluoride/acetonitrile was added, giving a slow temperature incre ie of 50 and a return to room temperature during a period of 1 h. A sample was removed for analysis. NMR showed no residual monomer. GPC showed Mn 3910, Mw 4570, D=1.17 (theor.

3200). The solution was treated with 2 mL of hydrochloric acid in methanol, and after 30 min the polymer was precipitated with aqueous methanol to give 10.35 g of PMMA with a terminal carboxylic acid group. Anal. Acid Number Calcd for M 3910: 14.32 mg 0* 6 KOH/g. Found: 13.70, 14.38 mg KOH/g. NMR showed S .that the olefinic end group of the polymer resulted .i from 71% substitution at the 2-position of the initiator to give 2 diasteromers (multiplets at 5.1, I' 15 5.89, and 6.08 ppm) and 29% substitution at the 4-position of the initiator giving a conjugated acid (multiplets at 2.48, broad CH 2 and 6.72 ppm).

34

Claims (18)

1. Group Transfer Polymerization process comprising contacting under polymerizing conditions at least one acrylic monomer with a tetracoordinate organosilicon, organotin or organogermanium polymerization initiator having at least one initiating site and (ii) a co-catalyst which is at osourco or 1flf]11orldi, f luo ride, cyanide or azide ions or a suitable Lewis acid, Lewis base or selected (bi)oxyaniono the process further characterized in 10 that: Mi the monomer Comprises one or more polyenoate compounds of the formula Cfl(R 2 )C(R 3 4 5 1] n c(o)x; or (ii) the initiatlor comprises one or more 15 polyenolates of the formula Q 2 COR 3 4 n or C-silylated isomers thereof; or (Iii) the monomer comprises one or more polyenoate compouinds of the formula CH(R )=C(IR J H- C(O)X and the initiator 20 comprises one or more polyenolates of the formula Q fcMR 4 n Q or C-sllylated isomers thereof wherein; R 2 is: -11 or 25 a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatirc-aromotic radical Containing up to 20 carb,; atoms; a polymeric hydrocarbyl radical containing at least 20 carbon atoms; a radical. of or containing one or more ether oxygen atoms within aliphatic segments thereofP or a radlical. of or con- taining one or more functional substitu- 0 00 00 0 0 0 00 0 0 ~0 00 00 00 0 0 0 0 00~ tot o 36 ents that are inert under polymerizing each of R, R and R ,independently, is H or a radical as defi.ned in and for R 2 or R 2 and the 4 3 5 closest R tDr R and the closest R or the two closest R 0 groups, or the two close' R 5 groups, talten together, form a ring structure co~ntaining at least carbon atoms or at least 5 carbon atoms and a heteroatom selected from -N- 444and the heteroatom being substituted with R' defined as below; X is -OR or 155 and (e f~ir or R and the closest taken together, form a 5- to 8-membered lactone ring; each of R' and Pa', independently, isC alkyl; and n is on integer and is at least 1; provided, however: when n is 1, at least one of R2 R 4and R 5 is hydricarbyl; 2S (ii) the number of R 2 5 hydrocarbyl substitu' ,nts does not exceed the number of -C-C- double bonds; and (iii) a car bon atom substituted with R 25hydrocarbyl is not adjacent to more than one other carbon atom substituted with R 2 5 hydrocarbyl, hydrocarbyl in (ii) and (iii) being as defined above in and for R 2 Q 1is -C(R 5 kC(QM(R I1 3 2 Q~ 2i C(R 2 0MtR 1 1 or -R 2 X, is -OSi(R 1 3 -OR or 31 each R 1 independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic, or mixed aliphatic- aromatic radical containing up to carbon atoms; and M is Si, Sn or Ge; provided, however, in the initiator of the formula Q2C(R 3)=C(R4 )nQ 1or C-silylated isomers thereof no. n 4 more than one of R and the closest R is 1 0 hydrocarbyl; and when Q2 is -(R2)=C(X')OM[R 1 3, not Smore than one of R and the adjacent is 0 o hydrocarbyl. 2

2. Process of Claim 1 wherein R or R is S. hydrocarbyl. 15 5

3. Process of Claim 1 wherein R is hydro- carbyl.

4. Process of Claim 1 wherein at least one 2-5 of R, aind R is methyl. Process of Claim 1 wherein at least one 2-5 20 of R, and R 5 is ethyl.

6. Process of Claim 1 wherein X is -OR and n is 1-3.

7. Process of Claim 1 wherein the monomer comprises one or more polyenoates.

8. Process of Claim 1 wherein the initiator comprises one or nore polyenolates. t 9. Product of the process of Claim 1. "Living" polymer comprising: at least three repeat units of the 3 0 formula -CH(R2 )CR3 )C(R 4 or (ii) at least three repeat units of a Group Transfer Polymerization acrylic monomer; or (iii) a mixture of at least thre- repeat units of and (ii); 3 3 each of (ii) and (iii) containing 38 -M(R )3 moieties at "living" ends of the polymer chains; and at non-living ends of the polymer chains, a saturated hydrocarbyl radical, or the unsaturated iety R2C(R3 )C(R4 )nC(R5)(C(O)X' provided, however, only the unsaturated moiety when the "living" polymer contains only repeat units (ii), wherein: hydrocarbyl radical is as defined in for R 2 below; 2 So R 2 is: -H or -C(O)X; a hydrocarbyl radical which is an 15 aliphatic, alicyclic, aromatic or mixed aliphatic-arqmatic radical containing up to 20 carbon atoms; a polymeric hydrocarbyl radical containing at least 20 carbon atoms; a radical of or containing one or more ether oxygen atoms within aliphatic segments thereof; or a radical of or con- taining one or more functional substitu- ents that are inert under polymerizing conditions; each of R 3 R and R 5 independently, is -H or a radical as defined in and for R2; or R 2 and the closest R 4 or R 3 and the closest R or the two closest R 4 groups, or the two closest R 5 groups, taken together, form a ring structure containing at least carbon atoms or at least 5 carbon atoms and a heteroatom selected from -N- It 39 and the heteroatom being substituted with R' defined as below; X is -OR or -NR'R"; each R 1 independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic, or mixed aliphatic- aromatic radical containing up to carbon atoms; and R is a radical as defined in (d) and for R2; or R and the closest R taken together, form a 5- to 8-membered 01 lactone ring; V#4 each of R' and independently, is C1-4 S: alkyl; i 15 M is Si, Sn or Ge; and ir n is an integer and is at least 1; provided, however: when n is 1, at least one of R, R and R is hydrocarbyl; (ii) the number of R 2 hydrocarbyl substituents does not exceed the number of -C-C- double bonds; and (iii) a carbon atom substituted with R 2 5 hydrocarbyl is not adjacent to more than one other carbon atom substituted with R 2 5 hydrocarbyl, hydrocarbyl in (ii) and (iii) being as defined above in and for R

11. "Living" polymer of claim 10 which includes central segments of the formula R 2 R 3 R 4 R I I I I -c nc- I I cox' cox' w i wherein R 2 5 and n are as defined is -OSi(R 1 )3 -OR or -NR'R" wh R" are as defined in Claim

12. Polymer of Claim 10 r. la ll--~ur, in Claim 10 and X' 1 erein R, R R' and wherein M is Si. S4 Cp t 44~

13. Polymer

14. Polymer hydrocarbyl. Polymer hydrocarbyl. 160

16. Polymer hydrocarbyl.

17. Polymer hydrocarbyl.

18. Polymer 1 one of R 2 5 is methyl

19. Polymer 2-5 one of R 2 5 is methyl Polymer are -OR and n is 1 to

21. Polymer are -OR and n is 1 to

22. Polymer or ethyl. of Claim 11 of Claim 10 of Claim 11 of Claim 14 of Claim 15 of Claim 10 or ethyl. of Claim 11 or ethyl. of Claim 14 3. of Claim 15 3. of Claim 20 wherein wherein wherein wherein wherein wherein wherein wherein wherein wherein wherein M is Si. 2 5 R or R is 2 5 R 2 or R is R 5 is R 5 is at least at loast X and X' X and X' R is methyl R is methyl 23. Polymer of Claim 21 or ethyl.

24. A Group Transfer Polymerization process substantially as hereindescribed with reference to the Examples. A polymer when produced by the process claimed in any one of claims 2 to 8 or 24. DATED this 18 day of January 1988. JAMES M. LAWRIE .Q Pd'en( Attorneys for E.I. DU PONT DE NEMOURS AND COMPANY